Ammonia from nickel/sodium

Other aqueous preparative methods include aerial oxidation of an alkaline solution of CoS04 and NaCNO to give the fulminatocobaltate(III) anion [Co(CNO)6]3-, reduction of ruthenate(VI) by excess of fulminate to give [Ru(CNO)6]4, and displacement of 2,2 -bipyridyl or 1,10-phenan-throline from nickel(II) or cobalt(III) complexes to give [Ni(CNO)4]2 or [Co(CNO)6]3. Liquid ammonia may replace water as solvent [Ni(NH3) ]2+ and [Co(NH3)6]3+, for example, react with sodium fulminate in this solvent to form [Ni(CNO)4]2 and [Co(CNO)6]3. In all these reactions fulminate behaves very like cyanide with [AuClJ-, however, reduction to form the gold(I) complex [Au(CNO)2] takes place and no gold(III) complex can be isolated. 

Sodamide.—This is prepared by the action of ammonia gas on sodium heated to 300°—400°. For the preparation of quantities of 20 gms. or more the most convenient apparatus consists of some form of closed iron pot provided with inlet and outlet tubes for ammonia. The apparatus, Fig. 37, or an autoclave from which any copper fittings have been removed, can easily be adapted to suit the purpose. If the apparatus is free from rust, the sodium may be placed directly on the bottom of the pot. Or, it may be contained in a large nickel or iron crucible. Before commencing to heat, the air should be displaced from the pot by ammonia, after which the temperature is raised to and maintained at 300°— 400° while a current of the dry gas is passed over the molten metal. The reaction takes place readily. If, after cooling and opening the pot, any soft lumps of sodium remain on the surface, these can be picked out with a knife, or else the apparatus may be closed again and more ammonia passed over the heated metal. The sodamide forms a hard mass which is chipped out with a knife or chisel. It is now available commercially and should be preserved in stoppered bottles. 

Amino-5-deoxy-l,2-0-isopropylidene-a-D-xylofuranose (15) can be prepared by the reaction of I,2-0-isopropylidene-5-0-p-tolyl-sulfonyl-a-D-xylofuranose with ammonia "or with sodium azide" or, more readily and in better yield, from the readily available 1,2-0-isopropylidene-a-D-glucofuranose by reaction with periodate to form the pentodialdofuranose derivative (13) whose phenylhydrazone (14) can be reduced to compound 15 with hydrogen in the presence of Raney nickel. "... 

The reaction of 48 (R = CH2Br) with primary aliphatic amines afforded the appropriate iV-substituted 3-benzazepine.32 It has been reported12 that 35 (R -R8 = H) could not be prepared by eliminating ammonia from 40 (R = CH2NH2) and that the reduction of 40 (R = CN) with sodium in alcohol gave 41 and 40 (R = CH2NH2), respectively.33 However, when the reduction of 40 (R = CN) was carried out over Raney nickel... 

Development of the Jarosite process in the zinc industry in the 1960s led to an understanding that iron could be precipitated from nickel laterite atmospheric leach solutions, at moderate acid levels, by the addition of an alkali such as potassium, sodium, or ammonia, whilst maintaining a temperature in excess of 90°C [4]. 

A problem with sodium hypochlorite is its ability to chlorinate some compounds to form volatile reaction products. Ammonia and alkylamines, for example, can be chlorinated to form chloramines. The problem can be avoided by removing alkaline nitrogen compounds from the gas stream with an acid wash prior to the sodium hypochlorite scrubber. An alternative approach described by Valentin (1990) is the use of a catalyst in the scrubber liquid to promote oxidation. Hydrated nickelic oxide, which is formed in solution from nickel sulfate and sodium hypochlorite at a pH of 9 to lO.S, is recommended. A nickel concentration of 50-75 ppm is said to be effective, making removal of up to 95% of the odorous compounds possible in a single stage. 

Fast sulphon black F ( C.I.26990). This dyestuff is the sodium salt of 1-hydroxy-8-( 2-hydroxynaphthylazo) -2- (sulphonaphthylazo) -3,6-disulph onic acid. The colour reaction seems virtually specific for copper ions. In ammoniacal solution it forms complexes with only copper and nickel the presence of ammonia or pyridine is required for colour formation. In the direct titration of copper in ammoniacal solution the colour change at the end point is from magenta or [depending upon the concentration of copper(II) ions] pale blue to bright green. The indicator action with nickel is poor. Metal ions, such as those of Cd, Pb, Ni, Zn, Ca, and Ba, may be titrated using this indicator by the prior addition of a reasonable excess of standard copper(II) solution. 

Synthesis. The trimetalic nickel binary pz (75) was prepared from 69a (Scheme 14) (22). Porphyrazine 69b was reductively deprotected with sodium in ammonia then reprotected forming 74, which allowed for purification of the molecule. The pivolyl protecting group was cleaved by saponification with sodium methoxide and the dithiolate, in situ, was reacted with NiCl2-6H20 to yield the binary pz complex 75. 

Consequently, by choosing proper conditions, especially the ratios of the carbonyl compound to the amino compound, very good yields of the desired amines can be obtained [322, 953]. In catalytic hydrogenations alkylation of amines was also achieved by alcohols under the conditions when they may be dehydrogenated to the carbonyl compounds [803]. The reaction of aldehydes and ketones with ammonia and amines in the presence of hydrogen is carried out on catalysts platinum oxide [957], nickel [803, 958] or Raney nickel [956, 959,960]. Yields range from low (23-35%) to very high (93%). An alternative route is the use of complex borohydrides sodium borohydride [954], lithium cyanoborohydride [955] and sodium cyanoborohydride [103] in aqueous-alcoholic solutions of pH 5-8. 

The vendor claims that the following metals have been successfully treated to parts per biUion (ppb) and detection limit levels aluminum, arsenic, cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, molybdenum, nickel, selenium, silver, tin, uranium, vanadium, and zinc. The system is also able to remove ammonia, nitrates, phosphates, potassium, fluorides, and sodium. Studies have also been performed using Aqua-Fix to remove radionuchdes such as uranium from waste streams. 

Additive or more-than-additive toxicity of free cyanide to aquatic fauna has been reported in combination with ammonia (Smith et al. 1979 Leduc et al. 1982 Alabaster et al. 1983 Leduc 1984) or arsenic (Leduc 1984). However, conflicting reports on the toxicity of mixtures of HCN with zinc or chromium (Towill et al. 1978 Smith et al. 1979 Leduc et al. 1982 Leduc 1984) require clarification. Formation of the nickelocyanide complex markedly reduces the toxicity of both cyanide and nickel at high concentrations in alkaline pH. At lower concentrations and acidic pH, solutions increase in toxicity by more than 1000-fold, owing to dissociation of the metallo-cyanide complex to form hydrogen cyanide (Towill et al. 1978). Mixtures of cyanide and ammonia may interfere with seaward migration of Atlantic salmon smolts under conditions of low dissolved oxygen (Alabaster et al. 1983). The 96-h toxicity of mixtures of sodium cyanide and nickel sulfate to fathead minnows is influenced by water alkalinity and pH. Toxicity decreased with increasing alkalinity and pH from 0.42 mg CN/L at 5 mg CaCOj/L and pH 6.5, to 1.4 mg CN/L at 70 mg CaCOj/L and pH 7.5 to 730 mg CN/L at 192 mg CaCOj/L and pH 8.0 (Doudoroff 1956). 

Dicyclopentadienyldinickeldiphenylbutadiyne-dicobalt hexacarbonyl has been prepared from diphenyldiacetylene in which one triple bond acts as a bridging group between two nickel atoms and the other between two cobalt atoms (203). Reduction of the diphenylacetylene complex (R = R = Ph) with sodium and alcohol in liquid ammonia yields dibenzyl, showing that the diphenylacetylene grouping is bonded only to the nickel atoms. The corresponding complex of acetylene (R = R = H) has also been prepared from nickeloccne and acetylene (69) ... 

Tetrammino-nickel Nitrite, [Ni(NH3)4](N02)2, is formed by the action of ammonia on a mixture of aqueous nickel sulphate and sodium nitrite at 22° C. After standing for some time a crystalline precipitate is deposited. The substance crystallises in small cherry-red monoclinic crystals which dissolve in cold water, forming a green solution. The solution soon becomes cloudy owing to decomposition of the salt. Even in moist air the salt decomposes, loses ammonia, and changes in colour. The colour of the compound is peculiar to this one salt, a fact remarked upon by Ephraim, who assumes for the compound a different constitution from the other nickel ammino-salts. He suggests the... 

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